TWI631074B - Mixtures of aluminum hydrogenphosphites with aluminum salts, process for preparation thereof and use thereof - Google Patents

Abstract

The invention relates to a mixture of aluminum hydrogen phosphite of formula (I) Al _2.00 (HPO ₃ ) _v (H ₂ PO ₃ ) _y x (H ₂ O) _z (I) and an aluminum salt, which contains 91 to 99.9% Aluminum hydrogen phosphite of formula (I) 0.1 to 9% aluminum salt, and 0 to 50% water (crystal water) where v in formula (I) is 2 to 2.99, y is 2 to 0.01 and z is 0 to 4 , Its preparation method and its use.

Description

Mixture of aluminum hydrogen phosphite and aluminum salt, preparation method thereof, and use thereof

The invention relates to a mixture of aluminum hydrogen phosphite and an aluminum salt, a preparation method thereof, and uses thereof.

It has been known that pure aluminum phosphite is basically a porous compound that has a three-dimensional network of zeolite-like structures in which aluminum ions and phosphite ions form a multi-membered ring. It may contain crystalline water or crystalline release water that loses crystal structure and thus forms an anhydrous substance. According to the prior art, crystallization is carried out hydrothermally, that is, above its boiling point at the autogenous pressure. To help with crystallization (Yang. Shiyou Xuebao, Shiyou Jiagong (2006), 22 (Suppl.), 79-81), a polynitrogen compound is added as a structure directing agent-also called a template.

The present invention relates to a mixture of aluminum hydrogen phosphite and an aluminum salt. These aluminum hydrogen phosphites contain a significant mole ratio of protonated phosphite ions bound to the substance.

It has been found that, surprisingly, the mixture of aluminum hydrogen phosphite and aluminum salt according to the invention can be used as a synergist for flame retardants. These flame retardant synergists do not have to be flame retardant by themselves, but can significantly improve the effectiveness of the flame retardant. Basically, flame retardant synergists are mixed with flame retardants and other polymer additives by kneading and extruding with polymers. This takes place at a temperature at which the polymer is in a molten form and this can significantly exceed 320 ° C. for a short time. The flame retardant synergist must be able to withstand these temperatures and not decompose in order to finally obtain a flame retardant polymer mixture. Present It was surprisingly found that the thermal stability of the mixture of aluminum hydrogen phosphite and aluminum salt of the present invention is significantly better than pure aluminum phosphite.

In addition, the prior art discloses aluminum phosphite hydrates, but these adversely release water upon heating and therefore affect the synergist in a disruptive manner to obtain flame-retardant polymers during processing. Another object of the invention is to prevent this water from being released. This object is achieved by the mixture of aluminum hydrogen phosphite and aluminum salt according to the present invention, and therefore the mixture is substantially free of crystal water.

Also known is a mixture of aluminum hydrogen phosphite and aluminum hydroxide. The disadvantage is that the aluminum hydroxide content reduces the active phosphite content. The purpose of the present invention is to achieve the highest active phosphite content by using the mixture of aluminum hydrogen phosphite and aluminum salt according to the present invention. Therefore, the content of specific phosphite with monovalent phosphorus ion in the salt is higher than that with divalent phosphorus ion. The reason for the compounds. In addition, the thermal stability of the mixture of aluminum phosphite and aluminum hydroxide is inferior to the mixture of aluminum hydrogen phosphite and aluminum salt of the present invention.

Therefore, the present invention relates to a mixture of aluminum hydrogen phosphite of formula (I) Al _2.00 (HPO ₃ ) _v (H ₂ PO ₃ ) _y x (H ₂ O) _z (I) and an aluminum salt, comprising 91 to 99.9% by weight aluminum biphosphite of formula (I) 0.1 to 9% by weight aluminum salt, and 0 to 50% by weight water (crystal water) where v in formula (I) is 2 to 2.99, y is 2 to 0.01 and z is 0 to 4.

Preferably, v is 2.56 to 2.99, y is 0.9 to 0.02, and z is 0 to 1. More preferably, v is 2.834 to 2.99, y is 0.332 to 0.03, and z is 0.01 to 0.1.

A mixture of aluminum hydrogen phosphite and aluminum salt, such as one or more of items 1 to 6 of the patent application, preferably having a particle size of 0.1 to 1000 microns and a solubility in water of 0.01 g / l to 10 g / Liter, bulk density is 80 to 800 grams / liter, and residual moisture content is 0.1 to 5%.

Preferably, the aluminum salt is aluminum metal, aluminum alloy, oxide, hydroxide, peroxide, peroxide hydrate, carbonate, percarbonate, mixed carbonate / hydrate, formate, Acetate, propionate, stearate, lactate, ascorbate, oxalate, or an aluminum salt with an anion of an acid having a vapor pressure higher than that of phosphorous acid.

This standard is also achieved by a method of manufacturing a mixture of aluminum bisulfite and aluminum salts such as one or more of the items in the scope of application for patents, which includes a phosphorus source with a ratio of 2.5 to 3.5 moles and 2 moles. The aluminum source is reacted at a temperature of 50 to 300 ° C without using a solvent.

Preferably, the reaction is performed at 120 to 220 ° C.

Preferably, the aluminum source is aluminum metal, aluminum alloy, oxide, hydroxide, peroxide, peroxide hydrate, carbonate, percarbonate, mixed carbonate / hydrate, formate, Acetate, propionate, stearate, lactate, ascorbate, oxalate, or an aluminum salt with an anion of an acid having a vapor pressure higher than that of phosphorous acid.

Preferably, the phosphite source is phosphorous acid, phosphorus trioxide, phosphorus trichloride, phosphorus element and / or hypophosphorous acid.

The present invention also relates to the use of a mixture of aluminum hydrogen phosphite and an aluminum salt, such as at least one of claims 1 to 6, as an intermediate for further synthesis, as an adhesive, and in an epoxy resin. In the curing of polyurethane and unsaturated polyester resins, it can be used as a crosslinking agent or accelerator, as a polymer stabilizer, as a crop protection composition, as a chelating agent, as a mineral oil additive, and as a resist. For cleaning and cleaning composition applications and for electronic applications.

The invention particularly relates to the use of a mixture of aluminum hydrogen phosphite and an aluminum salt, such as at least one of claims 1 to 6, in particular as a flame retardant, especially as a flame retardant for transparent coatings and intumescent coatings. As a flame retardant for wood and other cellulose products, as a reactive and / or non-reactive flame retardant for polymers, for the manufacture of flame retardant polymer molding compositions, for the manufacture of flame retardant polymers Molded and / or used to impart flame retardancy to polyester and pure and blended cellulosic fabrics by impregnation, and as a synergist in flame retardant mixtures.

The invention also includes a flame retardant thermoplastic or thermosetting polymer molded Composition and polymer molding, film, filament, and fiber, comprising 0.1 to 45% by weight of a mixture of aluminum hydrogen phosphite and an aluminum salt such as at least one of items 1 to 6 of the patent application range, 55 to 99.9 Wt% thermoplastic or thermosetting polymers or mixtures thereof, 0 to 55 wt% additives and 0 to 55 wt% fillers or reinforcing materials, where the sum of these components is 100 wt%.

The present invention also relates to a flame-retardant thermoplastic or thermosetting polymer molding composition and polymer molding, film, filament, and fiber, which contains 0.1 to 45% by weight and contains 0.1 to 50% by weight. A mixture of aluminum hydrogen phosphite and an aluminum salt of at least one of items 1 to 6 and a flame retardant mixture of 50 to 99% by weight of a flame retardant, 55 to 99.9% by weight of a thermoplastic or thermosetting polymer or a mixture thereof, 0 to 55 wt% additive and 0 to 55 wt% filler or reinforcing material, where the sum of these components is 100 wt%.

Preferably, the flame retardant comprises a dialkyl phosphinic acid and / or a salt thereof; a condensation product of melamine and / or a reaction product of melamine and phosphoric acid and / or a reaction product of a condensation product of melamine and polyphosphoric acid or a mixture thereof; Nitrogen-containing phosphate of formula (NH ₄ ) _y H _3-y PO ₄ or (NH ₄ PO ₃ ) _z , where y is 1 to 3 and z is 1 to 10,000; benzoguanamine, ginseng (hydroxyethyl ) Isocyanurate, allantoin, glycoluril, melamine, melamine melamine, dicyandiamide, and / or guanidine; magnesium oxide, calcium oxide, oxidation Aluminum, zinc oxide, manganese oxide, tin oxide, aluminum hydroxide, boehmite, dihydrotalcite, hydrocalumite, magnesium hydroxide, calcium hydroxide, zinc hydroxide, oxidation Tin hydrate, manganese hydroxide, zinc borate, basic zinc silicate and / or zinc stannate.

More preferably, the flame retardant comprises melam, melem, melon, dimelamine pyrophosphate, melamine polyphosphate, melamamine polyphosphate , Melamine polyphosphate and / or meleramine polyphosphate and / or mixed poly salts and / or ammonium hydrogen phosphate, ammonium dihydrogen phosphate and / or ammonium polyphosphate.

Preferred flame retardants are also aluminum hypophosphite, zinc hypophosphite, calcium hypophosphite, sodium phosphite, monophenyl phosphinic acid and its salts, dialkyl phosphinic acid and its salts with monoalkyl phosphinic acid. And mixtures thereof, 2-carboxyethylalkyl phosphinic acid and its salts, 2-carboxyethylmethyl phosphinic acid and its salts, 2-carboxyethylaryl phosphinic acid and its salts, 2- Carboxyethylphenyl phosphinic acid and its salts, oxa-10-phosphaphenanthrene (DOPO) and its salts and adducts on p-benzoquinone, or itaconic acid and its salt.

Preferably, the content of crystal water is in the range of 0-5 wt%, especially 0-1 wt%.

Preferred alkali metal sources are, for example, alkali metal salts.

Preferably, the overall density of the mixture of aluminum hydrogen phosphite and aluminum salt of the present invention is 200 to 700 g / l.

The L color value of the mixture of aluminum hydrogen phosphite and aluminum salt of the present invention is preferably 85 to 99.9, more preferably 90 to 98.

The a color value of the mixture of aluminum hydrogen phosphite and aluminum salt of the present invention is preferably -4 to +9, and more preferably -2 to +6.

The b-color value of the mixture of aluminum hydrogen phosphite and aluminum salt of the present invention is preferably -2 to +6, more preferably -1 to +3.

The color values are shown in the Hunter system (CIE-LAB system, Commission Internationale d'Eclairage). L values range from 0 (black) to 100 (white), a values from -a (green) to + a (red), and b values from -b (blue) to + b (yellow).

A preferred source of phosphite is phosphorous acid or a precursor thereof. Substances that can form phosphite ions under process conditions, such as phosphorus trioxide (P ₂ O ₆ ) (which can form phosphorous acid under hydrolysis conditions), phosphorus trichloride, elemental phosphorus, or hypophosphorous acid (which It can be converted into phosphorous acid by oxidation).

It is an object of the present invention to provide a template-free mixture of aluminum hydrogen phosphite and an aluminum salt. Another object is to provide a method that does not require a template or an aqueous suspension.

Preferred reaction conditions are a temperature of from 0 to lines 300 ℃, more preferably from 50 to 170 ℃, and the reaction time is from 10 ^-7 to 10 ² hours. The pressure may be between 1 and 200 MPa (= 0.00001 to 200 bar), preferably between 10 Pa and 10 MPa.

Preferably, the energy input is 0.083 to 10 kW / m3, and more preferably 0.33-1.65 kW / m3.

The preferred reaction method is to initially introduce the aluminum source and meter it into the phosphite source. In an alternative preferred reaction mode, the aluminum source and the phosphite source are metered in simultaneously.

The reaction mixture is curable. Therefore, the preferred one is a multi-stage procedure: preliminary reaction in a reactor (e.g., kneader, mixer, rotating tube) to obtain solid material, and grinding (e.g., mill, kneader, Rotary tube), followed by heat treatment in a reactor (eg, kneader, mixer, rotary tube).

Alternatively, the full reaction can be performed in a heated grinding apparatus.

Preferably, the source of phosphite and source of aluminum are metered into the initial feed of the reaction mixture that has undergone the reaction.

The weight ratio of the reacted reaction mixture to the new material is from 1: 100 to 80:20, preferably from 30:70 to 70:30.

Preferably, a mixture of 1 to 50% by weight of aluminum hydrogen phosphite and an aluminum salt is initially introduced, and a mixture of 50 to 99% by weight of an aluminum source and a phosphite source is added (the molar ratio is 1.5 to 2.5 molar: 3 molar). ), Let it react at 20 to 300 ° C for 0.1 to 10 hours and thereafter let it react at 80 to 300 ° C for 0.9 to 10 hours.

Also preferably, a mixture of 2 to 20% by weight of aluminum hydrogen phosphite and an aluminum salt is initially introduced, and a mixture of 80 to 98% by weight of an aluminum source and a phosphite source is added (molar ratio is 1.9 to 2.1 mol: 3 mol). Ear), let it react at 50 to 270 ° C for 0.5 to 5 hours and then let it react at 100 to 180 ° C for 0.5 to 5 hours.

Preferably, the mixture of aluminum hydrogen phosphite and aluminum salt of the present invention is used as a flame retardant synergist.

Also preferred is a composition comprising 5 to 99.8% by weight of a mixture of aluminum hydrogen phosphite of formula (I) and an aluminum salt, 0.1 to 94.9% by weight of a dialkyl phosphinic acid or a salt thereof, and 0.1 to 30% by weight One or more polymer additives.

Preferred dialkylphosphinic acids and / or salts thereof are those of formula (II) Wherein R ¹ and R ^{2 are the} same or different and each is a linear or branched C ₁ -C ₆ -alkyl group; M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K, H; m is 1 to 4.

The preferred dialkyl phosphinates are aluminum diethyl phosphinate, aluminum methyl ethyl phosphinate, titanium bisdiethyl phosphinate, titanium diethyl phosphinate, bismethyl Titanyl ethyl phosphinate, titanium methyl ethyl phosphinate, zinc bisdiethyl phosphinate, zinc bismethyl ethyl phosphinate and mixtures thereof.

Suitable further flame retardants are in particular nitrogen compounds (DE-A-196 14 424, DE-A-197 34 437 and DE-A-197 37 727). Particularly suitable flame retardants correspond to formulae (III) to (VIII) or mixtures thereof

Where R ⁵ to R ⁷ are each hydrogen, C ₁ -C ₈ -alkyl, C ₅ -C ₁₆ -cycloalkyl or -alkylcycloalkyl, which may be hydroxyl functional or C ₁ -C ₄ -hydroxy Alkyl functional substitution, C ₂ -C ₈ -alkenyl, C ₁ -C ₈ -alkoxy, -fluorenyl, -fluorenyl, C ₆ -C ₁₂ -aryl or -aralkyl, -OR ⁸ and -N (R ⁸ ) R ⁹ , both of which are N-alicyclic and N-aromatic, R ⁸ is hydrogen, C ₁ -C ₈ -alkyl, C ₅ -C ₁₆ -cycloalkyl or- Alkylcycloalkyl, which may be substituted with hydroxyl functionality or C ₁ -C ₄ -hydroxyalkyl functionality, C ₂ -C ₈ -alkenyl, C ₁ -C ₈ -alkoxy, -fluorenyl,- Ethoxy or C ₆ -C ₁₂ -aryl or -aralkyl, R ⁹ to R ^{13 are the} same as R ⁸ and are also -OR ⁸ , m and n are each independently 1, 2, 3 or 4, X stands for acid, which is related to three Adduct of compound (III); or oligoester of (hydroxyethyl) isotricyanate and aromatic polycarboxylic acid.

Particularly suitable flame retardants are benzoguanamine, ginseng (hydroxyethyl) heterotrimer Cyanate, allantoin, glycoluril, melamine, melamine melamine, dicyandiamide, and / or guanidine.

Appropriate polymer additives for flame retardant polymer molding compositions and polymer moldings are UV absorbers, light stabilizers, lubricants, colorants, antistatic agents, nucleating agents, fillers, synergists Agents, fortifiers and others.

The flame retardant polymer molding of the present invention is preferably used as a lamp assembly, such as a lamp fitting and a lamp holder, a plug and a porous socket extension cord, a bobbin, a socket for a capacitor and a switch, and a circuit breaker. , Relay case and reflector.

The present invention also relates to an intumescent flame retardant coating comprising 1 to 50% by weight of a mixture of aluminum hydrogen phosphite of the present invention and an aluminum salt of formula (I) and 0 to 80% by weight ammonium polyphosphate, a binder, and foam formation Additives, fillers and polymer additives.

The intumescent flame retardant coating preferably contains 1 to 50% by weight of a mixture of aluminum hydrogen phosphite and an aluminum salt of the present invention and 0 to 80% by weight of ammonium polyphosphate, a binder, a foam former, and a dialkyl phosphonic acid. Salts, fillers and polymer additives.

The polymer is preferably derived from a thermoplastic polymer, such as a polyester, polystyrene or polyamide, and / or a thermosetting polymer.

The polymer is preferably a polymer of mono- and diolefins, such as polypropylene, polyisobutylene, polybutene-1, poly-4-methylpentene-1, polyisoprene or polyisoprene Butadiene, and cycloolefins (such as cyclopentene or Norbornene) addition polymers; and polyethylene (which can be optionally crosslinked), such as high density polyethylene (HDPE), high density high molecular weight polyethylene (HDPE-HMW), high density ultra-high density High molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE), and mixtures thereof.

The polymers are preferably copolymers of mono- and diolefins with each other or with other vinyl monomers, such as ethylene-propylene copolymers, linear low-density polyethylene (LLDPE), and their low-density polyethylene (LDPE) Mixture, propylene-butene-1 copolymer, propylene-isobutylene copolymer, ethylene-butene-1 copolymer, ethylene-hexene copolymer, ethylene-methylpentene copolymer, ethylene-heptene copolymer, Ethylene-octene copolymer, propylene-butadiene copolymer, isobutylene-isoprene copolymer, ethylene-alkyl acrylate copolymer, ethylene-alkyl methacrylate copolymer, ethylene-vinyl acetate copolymer, and Its copolymers with carbon monoxide, or ethylene-acrylic acid copolymers and their salts (ionomers), and the three copolymers of ethylene with propylene and dienes (such as hexadiene, dicyclopentadiene, or ethylidene norbornene) Polymer; and mixtures of this copolymer with each other, such as polypropylene / ethylene-propylene copolymer, LDPE / ethylene-vinyl acetate copolymer, LDPE / ethylene-acrylic acid copolymer, LLDPE / ethylene-vinyl acetate copolymer, LLDPE / Ethylene-acrylic acid copolymers and alternating or random polyalkylenes / a Carbon oxide copolymers and mixtures thereof with another polymer, such as polyamide.

The polymer is preferably a hydrocarbon resin (such as C ₅ -C ₉ ), including its hydrogenated modifiers (such as tacky resins) and mixtures of polyalkylenes and starch.

The polymer is preferably polystyrene (Polystyrol® 143E (BASF)), poly (p-methylstyrene), poly (α-methylstyrene).

The polymer is preferably a copolymer of styrene or α-methylstyrene and a diene or acrylic derivative, such as styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate , Styrene-butadiene-acrylic acid and alkyl methacrylates, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; styrene copolymers and other polymers (e.g. polyacrylates, Ene polymers or ethylene-propylene-diene terpolymers) and more impact-resistant mixtures; and block copolymers of styrene, such as styrene-butadiene-styrene, styrene-isoprene-benzene Ethylene, styrene-ethylene / butene-styrene or styrene-ethylene / propylene-styrene.

The polymer is preferably a graft copolymer of styrene or alpha-methylstyrene, such as styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile Copolymer, styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on On polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene, benzene Ethylene and alkyl acrylate or methacrylate on polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene terpolymer, styrene and acrylonitrile on polyalkyl acrylate or polymethacrylic acid Alkyl esters, styrene and acrylonitrile on acrylate-butadiene copolymers, and mixtures thereof, are called, for example, ABS, MBS, ASA or AES polymers.

The styrene polymer is preferably a relatively coarse-celled foam such as EPS (expanded polystyrene) such as Styropor (BASF) and / or a foam with relatively small cells such as XPS (extruded rigid polystyrene foam) ), Such as Styrodur® (BASF). Preferred are polystyrene foams such as Austrotherm® XPS, Styrofoam® (Dow Chemical), Floormate®, Jackodur®, Lustron®, Roofmate®, Styropor, Styrodur®, Styrofoam®, Sagex®, and Telgopor®.

The polymer is preferably a halogenated polymer such as polychloroprene, chloro rubber, chlorinated and brominated copolymers of isobutylene-isoprene (halobutyl rubber), chlorinated or chlorine Sulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, homo- and copolymers of epichlorohydrin, especially polymers of halogenated vinyl compounds, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride , Polyvinylidene fluoride; and copolymers thereof, such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate, or vinylidene chloride-vinyl acetate.

The polymer is preferably derived from alpha, beta-unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates, polymethylmethacrylate, polyacrylamide, and impact butyl acrylate Ester-modified polyacrylonitrile, and copolymers of the monomers with each other or with other unsaturated monomers (e.g., acrylonitrile-butadiene copolymer, acrylonitrile-alkyl acrylate copolymer, acrylonitrile-alkyl alkoxylate) Alkyl alkyl ester copolymer, acrylonitrile-vinyl halide copolymer or acrylonitrile-alkyl methacrylate-butadiene terpolymer).

The polymer is preferably derived from an unsaturated alcohol and an amine or its amidino derivative. Biological or acetal, such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate or maleate, polyvinyl butyral, allyl polyphthalate, polyallyl Melamine; and copolymers thereof with olefins.

The polymer is preferably a homo- and copolymer of a cyclic ether, such as a polyalkylene glycol, polyethylene oxide, polypropylene oxide, or a copolymer thereof with diglycidyl ether.

The polymer is preferably a polyacetal, such as polyoxymethylene, and polyoxymethylene containing a comonomer such as ethylene oxide; a polyacetal modified by a thermoplastic polyurethane, acrylate, or MBS.

The polymer is preferably polyphenylene ether and polyphenylene sulfide and mixtures thereof with a styrene polymer or polyamide.

The polymers are preferably polyethers, polyesters and polybutadienes with two terminal hydroxyl groups and aliphatic or aromatic polyisocyanates and their precursor-derived polyurethanes.

The polymers are preferably polyamidoamines and copolyamides, which are derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or corresponding lactams, such as nylon 2/12, nylon 4 (poly -4-Aminobutyric acid, Nylon® 4 from DuPont), Nylon 4/6 (poly (butylene hexamethylene diamine), Nylon® 4/6 from DuPont), Nylon 6 (polyhexane Lactam, poly-6-aminohexanoic acid, Nylon® 6, from DuPont, Akulon® K122, from DSM; Zytel® 7301, from DuPont; Durethan® B 29, from Bayer), nylon 6 / 6 ((Poly (N, N'-hexylhexanediamine), Nylon® 6/6, Available from DuPont, Zytel® 101 from DuPont; Durethan® A30, Durethan® AKV, Durethan® AM, available from Bayer; Ultramid® A3, available from BASF), nylon 6/9 (poly (hexyl nonylamine)) , Nylon® 6/9 from DuPont), Nylon 6/10 (Poly (hexyl sebacamide), Nylon® 6/10 from DuPont), Nylon 6/12 (Poly (hexyl dodecane) Diamine), Nylon® 6/12, available from DuPont), nylon 6/66 (poly (hexyl sebacamide-co-caprolactam), Nylon® 6/66, available from DuPont), nylon 7 (poly-7-aminoheptanoic acid, Nylon® 7, available from DuPont), nylon 7,7 (polyheptyl heptadiamine, Nylon® 7,7, available from DuPont), nylon 8 (poly- 8-Aminocaprylic acid, Nylon® 8 from DuPont), Nylon 8,8 (Polyoctyloctanediamine, Nylon® 8,8 from DuPont), Nylon 9 (Poly-9-aminononyl) Acid, Nylon® 9, available from DuPont), Nylon 9,9 (polybenzenylnonanediamine, Nylon® 9,9, available from DuPont), Nylon 10 (poly-10-aminocapric acid, Nylon® 10, obtained from DuPont), nylon 10,9 (polydecyl sebacamide, Nylon® 10,9, obtained from DuPont), nylon 10, 10 (polydecyl sebacamide, Nylon® 10, 10, got DuPont), Nylon 11 (poly-11-aminoundecanoic acid, Nylon® 11, available from DuPont), Nylon 12 (polylauryllactam, Nylon® 12, available from DuPont, Grillamid® L20, available from Ems Chemie), aromatic polyamines derived from m-xylene, diamine, and adipic acid; polyamines made of diamine and iso- and / or terephthalic acid (polyhexyl isophthalamide, polyamine Polyhexyl paraphthalamide) and optionally an elastomer as a modifier (e.g. poly-2,4,4-trimethylhexyl paraphthalamide or poly-m-phenylene isophthalamide) Lamine. Block copolymers, olefin copolymers, ionomers, or chemically bonded or grafted elastomers of the foregoing polyamides and polyolefins; or with polyethers (e.g., with polyethylene glycol, polypropylene glycol, or polybutylene glycol) ). In addition, polyamines or copolyamides modified by EPDM (ethylene propylene-diene rubber) or ABS (acrylonitrile-butadiene-styrene); and polyamines ("RIM polymer Amine system ").

The polymer is preferably polyurea, polyimide, polyimide, imine, polyetherimide, polyester, imine, polyallantoin, and polybenzimidazole.

The polymer is preferably made from a dicarboxylic acid and a diol and / or a hydroxycarboxylic acid or a corresponding lactone (such as polyethylene terephthalate, polybutylene terephthalate (Celanex® 2500, Celanex® 2002 , Obtained from Celanese; Ultradur®, obtained from BASF), poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoate), and polyesters having hydroxyl terminal groups Polyether-derived block polyetheresters; and polyesters modified with polycarbonate or MBS.

The polymers are preferably polycarbonates and polyester carbonates, and polyfluorene, polyetherfluorene and polyetherketone.

Preferably, the polymer is a crosslinked polymer which is derived from aldehyde on the one hand and phenol, urea or melamine on the other hand, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resin.

The polymer is preferably a dry and non-dried alkyd resin.

The polymer is preferably an unsaturated polyester resin, which is derived from a copolyester of a saturated and unsaturated dicarboxylic acid and a polyhydric alcohol, and the vinyl compound is used as a cross-linking agent, and may also be a halogenated flame retardant Modified matter.

The polymer is preferably a crosslinkable acrylic resin derived from substituted acrylic esters, such as from epoxy acrylates, urethane acrylates, or polyester acrylates.

Preferably, the polymer is an alkyd resin, a polyester resin, and an acrylate resin, which are crosslinked by a melamine resin, a urea resin, an isocyanate, a trimeric isocyanate, a polyisocyanate, or an epoxy resin.

The polymer is preferably a crosslinked epoxy resin which is derived from an aliphatic, cycloaliphatic, heterocyclic or aromatic epoxypropyl compound, such as bisphenol A diglycidyl ether, bisphenol F The product of diglycidyl ether, which is crosslinked with or without accelerators by conventional hardeners such as anhydrides or amines.

The polymer is preferably a mixture (polyblend) of the aforementioned polymers, for example, PP / EPDM (polypropylene / ethylene-propylene-diene rubber), polyamide / EPDM, or ABS (polyamidamine / ethylene) -Propylene-diene rubber or acrylonitrile-butadiene-styrene), PVC / EVA (polyvinyl chloride / ethylene-vinyl acetate), PVC / ABS (polyvinyl chloride / acrylonitrile-butadiene) Styrene-styrene), PVC / MBS (polyvinyl chloride / methacrylate-butadiene-styrene), PC / ABS (polycarbonate / acrylonitrile-butadiene-styrene), PBTP / ABS ( Polybutylene terephthalate / acrylonitrile-butadiene-styrene), PC / ASA (polycarbonate / acrylate-styrene-acrylonitrile), PC / PBT (polycarbonate / polybutylene terephthalate) Diester), PVC / CPE (polyvinyl chloride / chlorinated polyethylene), PVC / acrylate (polyvinyl chloride / acrylate), POM / thermoplastic PUR (polyformaldehyde / thermoplastic polyurethane), PC / Thermoplastic PUR (polycarbonate / thermoplastic polyurethane), POM / acrylate (polyoxymethylene / acrylate), POM / MBS (polyoxymethylene / methacrylate-butadiene-styrene), PPO / HIPS (Polyphenylene ether / high impact polystyrene), PPO / PA 6,6 (polyphenylene ether / nylon 6,6) and copolymers, PA / HDPE (polyamine / high-density polyethylene), PA / PP (Polyamine / polyethylene), PA / PPO (polyamine / polyphenylene ether), PBT / PC / ABS (polybutylene terephthalate / polycarbonate / acrylonitrile-butadiene-styrene) And / or PBT / PET / PC (polybutylene terephthalate / polyethylene terephthalate / polycarbonate).

Suitable mixing units for the manufacture of polymer moulding compositions are uniaxial or single-screw extruders, such as those available from Berstorff GmbH, Hanover and / or Leistritz, Nuremberg, and with three-zone screws and / or short compression Multi-zone screw extruders for screws, and twin screw extruders, for example, available from Coperion Werner & Pfleiderer GmbH & Co. KG, Stuttgart (ZSK 25, ZSK 30, ZSK 40, ZSK 58, ZSK MEGA compounder 40, 50, 58, 70, 92, 119, 177, 250, 320, 350, 380) and / or from Berstorff GmbH, Hanover, Leistritz Extrusionstechnik GmbH, Nuremberg.

Useful mixing units are also co-kneaders (e.g. available from Coperion Buss Compounding Systems, Pratteln, Switzerland, such as MDK / E46-11D) and / or laboratory kneaders (MDK 46, available from Buss, Switzerland, which Effective screw length L = 11D).

Suitable mixing units are also ring extruders, such as those available from 3 + Extruder GmbH, Laufen, which have 3 to 12 rings with small screws rotating around the static core, and / or planetary drive extruders, such as available from Entex, Bochum, and / or aspirated extruder and / or segmented extruder and / or Maillefer screw.

Mixers with reversed twin screws can also be used, such as the Compex 37 and 70 models of Krauss-Maffei Berstorff.

In the case of a uniaxial extruder or a single screw extruder, the effective screw length of the present invention is 20 to 40D. In a multi-zone screw extruder (input zone (L = 10D), transition zone (L = 6D) In the case of the injection zone (L = 9D)), for example, 25D, and in the case of a twin-screw extruder, 8 to 48D.

Manufacturing, processing, and testing of flame-retardant polymer molding compositions and polymer moldings

The flame retardant component is mixed with polymer pellets and any additives and is subjected to a temperature of 230 to 260 ° C (PBT-GR) or 260 to 280 ° C (PA 66-) in a twin-screw extruder (model: Leistritz LSM 30/34). GR) Blend. row The homogenized polymer strips were placed, cooled in a water bath and pelletized afterwards.

After sufficiently drying, the molding composition was processed on an injection molding machine (model: Aarburg Allrounder) at a temperature of 240 to 270 ° C (PBT-GR) or 260 to 290 ° C (PA 66-GR) to obtain a sample.

Samples of each mixture were subjected to UL 94 combustion classification (Underwriter Laboratories) with 1.5 mm thick samples.

The UL 94 combustion classification is as follows: V-0: After the flame application is completed, the afterflame time has not exceeded 10 seconds, and the total afterflame time of 10 flames has not exceeded 50 seconds. There is no flame drop and the sample is not complete. After depletion, the afterglow time of the sample did not exceed 30 seconds.

V-1: After the application of the flame, the afterflame time does not exceed 30 seconds, and the total afterburning time of 10 times of the flame does not exceed 250 seconds. After the application of the flame, the embers time of the sample has not exceeded 60 seconds. Other standards are the same as V -0.

V-2: Cotton indicator is ignited by a falling flame. Other standards are the same as V-1.

Unable to rank (nc1): Cannot meet V-2 rating.

The composition (experimental) of aluminum hydrogen phosphite can be determined from P and Al analysis data. When the anionic charge is distributed between the divalent phosphite ion and the monovalent hydrogen phosphite ion, the sum of the cationic charge and the anionic charge is formed.

The composition of the mixture of aluminum salt and aluminum biphosphite can be determined, for example, by determining the residual phosphorus and aluminum in aluminum hydroxide and aluminum biphosphite samples using an x-ray powder diffractometer (reflection angle 2θ about 18.3 °). Measured. The latter was verified by the extremely low content of unconverted phosphorous acid.

Determination of unconverted phosphorous acid

To determine unconverted phosphorous acid, the resulting product (10% aqueous suspension) was refluxed at 100 ° C for 24 hours, then filtered, and the phosphorus content was determined, and this was used to calculate the H ₃ PO ₃ content in the sample.

Testing of thermal stability and phosphine formation

An important criterion for the thermal stability of the aluminum hydrogen phosphite of the present invention is the temperature at which a decomposition reaction occurs and a toxic PH ₃ is formed. The release of flame-retardant polymers must be avoided during the manufacturing period. For measurement, a material sample is heated in a tubular furnace under flowing nitrogen (30 liters / gram) by gradually increasing the temperature. When the Dräger detection tube can detect more than 1 ppm PH ₃ (short-term tube for hydrogen sulfide), it is regarded as reaching the decomposition temperature.

The invention is illustrated by the following examples. The quantities, conditions and analyses are listed in the table.

Example 1

1608.3 grams of aluminum hydroxide (Hydral® 710; ALCOA; 99.6%) was first introduced into the kneader. While mixing, 2864 grams of phosphorous acid (98%) were added in portions. The reaction occurred spontaneously and heat was released and the mixture was reacted at 150 ° C. The product contained 98.6 weight percent aluminum phosphite with a composition of Al ₂ (HPO ₃ ) _2.89 (H ₂ PO ₃ ) _0.22 , 1.4 weight percent aluminum hydroxide, and 0.25% by weight unconverted phosphorous acid.

Example 2

As in Example 1, aluminum hydroxide was reacted with phosphorous acid. The product contained 90.3% by weight of aluminum phosphite having a composition of Al ₂ (HPO ₃ ) ₂ (H ₂ PO ₃ ) ₂ , 9.7% by weight of aluminum hydroxide, and 0.45% by weight of phosphorous acid.

Example 3

As in Example 1, aluminum hydroxide was reacted with phosphorous acid. The product contained 99.6% by weight of aluminum phosphite having a composition of Al ₂ (HPO ₃ ) _2.97 (H ₂ PO ₃ ) _0.06 , 0.4% by weight aluminum hydroxide, and 0.05% by weight phosphorous acid.

Example 4 (comparative example)

Commercially available aluminum phosphites that are not of the present invention exhibit lower thermal stability (beginning to form PH _{3 at} 320 ° C).

Example 5

233 grams of a mixture of aluminum hydrogen phosphite and aluminum hydroxide was first introduced into the kneader. When mixing, 1787.2 grams (22.82 moles) of aluminum hydroxide (Hydral® 710; available from ALCOA; 99.6%) and 2864 grams (34.23 moles) of phosphorous acid (hence, aluminum and The ear ratio is 2: 3) and added to it in batches. Spontaneously reacts and releases heat. This mixture was allowed to react at 80 ° C for another 0.5 hours and then at 150 ° C for 2 hours. The product contained 98.8% by weight of aluminum phosphite having a composition of Al ₂ (HPO ₃ ) _2.84 (H ₂ PO ₃ ) _0.08 , 1.4% by weight aluminum hydroxide, and 0.2% by weight unconverted phosphorous acid.

Flame-retardant polymer molding composition and polymer molding

According to the general method for forming a flame-retardant polymer molding composition and a flame-retardant polymer molding, forming a UL-94 sample, 50% nylon 66 polymer, 30% glass fiber, 3.6 A weight% mixture of aluminum hydrogen phosphite and aluminum salt according to Example 1 and 16.4 weight% Exolit® OP1230 aluminum diethylphosphinate (available from Clariant). The UL-94 test is classified as V-0.

50% by weight polybutylene terephthalate, 30% by weight glass, according to the general method for forming a flame-retardant polymer molding composition and a flame-retardant polymer molding, forming a UL-94 sample Fiber, 3.6% by weight of a mixture of aluminum hydrogen phosphite and aluminum salt according to Example 1 and 16.4% by weight Exolit® OP1240 aluminum diethylphosphinate (available from Clariant). The UL-94 test is classified as V-0.

Claims (17)

A mixture of aluminum hydrogen phosphite of formula (I) Al _2.00 (HPO ₃ ) _v (H ₂ PO ₃ ) _y × (H ₂ O) _z (I) and an aluminum salt, comprising 91 to 99.9% of formula (I) Aluminum hydrogen phosphite, 0.1 to 9% aluminum salt, and 0 to 50% water (crystal water), where v in formula (I) is 2 to 2.99, y is 2 to 0.01 and z is 0 to 4, where The aluminum salt is an oxide, hydroxide, carbonate, percarbonate, or mixed carbonate / hydrate. For example, the mixture of item 1 in the patent application range, where v is 2.56 to 2.99, y is 0.9 to 0.02, and z is 0 to 1. For example, the mixture of item 2 in the patent application range, where v is 2.834 to 2.99, y is 0.332 to 0.03, and z is 0.01 to 0.1. A mixture according to any one of the claims 1 to 3, which comprises 95 to 99.9% by weight of aluminum hydrogen phosphite of formula (I), 0.1 to 5% by weight of an aluminum salt, and 0 to 50% by weight of water (crystal water). For example, the mixture of any one of items 1 to 3 in the patent application range has a particle size of 0.1 to 1000 microns, a solubility in water of 0.01 g / l to 10 g / l, and a bulk density of 80 to 800. G / l, and a residual moisture content of 0.1 to 5%. A method for producing a mixture of aluminum hydrogen phosphite and aluminum salt of formula (I) as in any one of claims 1 to 5 of the scope of patent application, which comprises allowing an aluminum source and a phosphite source to The reaction temperature is 300 ° C for 0.1 to 10 hours, wherein the aluminum source is aluminum oxide, hydroxide, carbonate, percarbonate, or mixed carbonate / hydrate, and wherein the phosphite source is phosphorous acid and And / or hypophosphorous acid. A use of a mixture of aluminum hydrogen phosphite and aluminum salt of formula (I) according to any one of claims 1 to 5 of the scope of patent application, as a polymer reactive and / or non-reactive flame retardant, To manufacture a flame-retardant polymer molding composition for manufacturing a flame-retardant polymer molding and / or for imparting flame retardancy to polyester and pure and blended cellulose fabrics by impregnation, and As a synergist in flame retardant mixtures. A flame-retardant thermoplastic or thermosetting polymer molding composition comprising 0.1 to 45% by weight of a mixture of aluminum hydrogen phosphite and an aluminum salt of formula (I) according to any one of claims 1 to 5, 55 to 99.9% by weight of a thermoplastic or thermosetting polymer or a mixture thereof, 0 to 55% by weight of an additive, and 0 to 55% by weight of a filler or reinforcing material, wherein the sum of these components is 100% by weight. A flame-retardant polymer molded article, film, filament, and / or fiber, comprising 0.1 to 45% by weight of aluminum hydrogen phosphite of formula (I) according to any one of claims 1 to 5 of the patent application scope and Mixtures of aluminum salts, 55 to 99.9% by weight thermoplastic or thermosetting polymers or mixtures thereof, 0 to 55% by weight additives and 0 to 55% by weight fillers or reinforcing materials, where the sum of these components is 100% by weight. A flame-retardant thermoplastic or thermosetting polymer molding composition comprising 01 to 45% by weight of hydrogen phosphite of formula (I) containing 01 to 50% by weight as in any one of claims 1 to 5 of the patent application scope Mixtures of aluminum and aluminum salts and flame retardant mixtures of 50 to 99.9% by weight flame retardants, 55 to 99.9% by weight of thermoplastic or thermosetting polymers or mixtures thereof, 0 to 55% by weight additives and 0 to 55% by weight fillers or reinforcements Materials, where the sum of these components is 100% by weight. A flame-retardant polymer molded article, film, filament, and / or fiber, which contains 0.1 to 45% by weight and contains 0.1 to 50% by weight. The formula (I) ) A mixture of aluminum hydrogen phosphite and aluminum salt and a flame retardant mixture of 50 to 99.9% by weight of a flame retardant, 55 to 99.9% by weight of a thermoplastic or thermosetting polymer or a mixture thereof, 0 to 55% by weight of an additive, and 0 to 55 % By weight filler or reinforcing material, where the sum of these components is 100% by weight. For example, a flame-retardant thermoplastic or thermosetting polymer molding composition in the scope of claim 8 or 10, wherein the flame retardant comprises a dialkyl phosphinic acid and / or a salt thereof; a condensation product of melamine and / or a melamine and Reaction product of phosphoric acid and / or reaction product of condensation product of melamine and polyphosphoric acid or mixture thereof; nitrogen-containing phosphate of formula (NH ₄ ) _y H _3-y PO ₄ or (NH ₄ PO ₃ ) _z , where y Is 1 to 3 and z is 1 to 10,000; benzoguanamine, ginseng (hydroxyethyl) isocyanurate, allantoin, glycoluril, melamine, melamine melamine Esters, dicyandiamide and / or guanidine; magnesium oxide, calcium oxide, aluminum oxide, zinc oxide, manganese oxide, tin oxide, aluminum hydroxide, boehmite, dihydrotalcite, Hydrocalumite, magnesium hydroxide, calcium hydroxide, zinc hydroxide, tin oxide hydrate, manganese hydroxide, zinc borate, basic zinc silicate, and / or zinc stannate. For example, the flame-retardant polymer moldings, films, filaments, and / or fibers in the scope of application for patent No. 9 or 11, wherein the flame retardant comprises a dialkyl phosphinic acid and / or a salt thereof; a condensation product of melamine And / or reaction products of melamine and phosphoric acid and / or reaction products of melamine condensation products and polyphosphoric acid or mixtures thereof; nitrogen-containing compounds of formula (NH ₄ ) _y H _3-y PO ₄ or (NH ₄ PO ₃ ) _z Phosphate, where y is 1 to 3 and z is 1 to 10,000; benzoguanamine, ginseng (hydroxyethyl) isocyanurate, allantoin, glycoluril, melamine, Melamine melamine, dicyandiamide and / or guanidine; magnesium oxide, calcium oxide, aluminum oxide, zinc oxide, manganese oxide, tin oxide, aluminum hydroxide, boehmite, dihydrate Dihydrotalcite, hydrocalumite, magnesium hydroxide, calcium hydroxide, zinc hydroxide, tin oxide hydrate, manganese hydroxide, zinc borate, basic zinc silicate, and / or zinc stannate. For example, the flame-retardant thermoplastic or thermosetting polymer molding composition of the scope of application for the patent No. 8 or 10, wherein the flame retardant comprises melam, melem, melamine ( melon), dimelamine pyrophosphate, melamine polyphosphate, melamine polyphosphate, melamine polyphosphate and / or meleramine polyphosphate and / or mixed polysalts and / or Ammonium hydrogen phosphate, ammonium dihydrogen phosphate, and / or ammonium polyphosphate. For example, a flame-retardant polymer molded article, film, filament, and / or fiber in the scope of application for patent No. 9 or 11, wherein the flame retardant includes melam, melem, trimer Melon, dimelamine pyrophosphate, melamine polyphosphate, melamine polyphosphate, melamine polyphosphate, and / or meleramine polyphosphate and / or mixtures thereof Polysalts and / or ammonium hydrogen phosphate, ammonium dihydrogen phosphate and / or ammonium polyphosphate. For example, the flame retardant thermoplastic or thermosetting polymer molding composition of the scope of application for patent No. 8 or 10, wherein the flame retardant comprises aluminum hypophosphite, zinc hypophosphite, calcium hypophosphite, sodium phosphite, and monophenylphosphine Acids and their salts, mixtures of dialkylphosphinic acids and their salts and monoalkylphosphinic acids and their salts, 2-carboxyethylalkylphosphinic acids and their salts, 2-carboxyethylmethylphosphine Acids and their salts, 2-carboxyethylaryl phosphinic acid and its salts, 2-carboxyethylphenyl phosphinic acid and its salts, oxa-10-phosphaphenanthrene (DOPO) and Its salts and adducts on p-benzoquinone, or itaconic acid and its salts. For example, a flame-retardant polymer molded article, film, filament, and / or fiber in the scope of application patent No. 9 or 11, wherein the flame retardant comprises aluminum hypophosphite, zinc hypophosphite, calcium hypophosphite, sodium phosphite, Monophenyl phosphinic acid and its salts, dialkyl phosphinic acid and its salts and mixtures of monoalkyl phosphinic acid and its salts, 2-carboxyethylalkyl phosphinic acid and its salts, 2-carboxyethyl Methylmethyl phosphinic acid and its salts, 2-carboxyethylaryl phosphinic acid and its salts, 2-carboxyethylphenyl phosphinic acid and its salts, oxa-10-phosphaphenanthrene ) (DOPO) and its salts and adducts on p-benzoquinone, or itaconic acid and its salts.